Part I, Diiridium(iii) porphyrins as carbon-carbon bond activation catalysts: Part II, Regioselective carbon-carbon bond activation of cyclopropanes by iridium(iii) porphyrins

This thesis reports on the results of my research project on carbon-carbon bond activation mediated by iridium porphyrin complexes. My project consists of two parts: (1) study of diiridium(III) porphyrins as catalysts for carbon-carbon bond activation, and (2) regioselective carbon-carbon bond activation of substituted cyclopropanes mediated by an iridium(III) porphyrin. ; In part 1 of my work, a series of diporphyrin compounds containing two porphyrin moieties conjoined with amide linkage were synthesized. Metalation of these diporphyrin compounds led to the isolation of the corresponding diiridium(III) diporphyrin complexes (Scheme 1). The reactivity of these diiridium(III) diporphyrin complexes towards hydrogenolysis of a carbon(sp3)-carbon(sp3) σ-bond of [2.2]paracyclophane using water as a hydrogen source was examined. It was found that the amide-linked diiridium diporphyrins exhibited poor catalytic activity due to hydrolysis of the conjoining amide linkage in water at elevated temperatures. ; In part 2 of my study, I have examined stoichiometric ring opening of cyclopropanes mediated by iridium porphyrin hydride complex Ir(ttp)H (ttp =5,10,15,20-tetra-(p-tolyl)porphyrin dianion). Results of my study revealed that cyclopropanes underwent ring opening from breaking the weakest bondthermodynamically, followed by 1,3-addition to the iridium porphyrin hydride bond togive the corresponding iridium porphyrin substituted propanes (Scheme 2). Catalytic carbon-carbon bond activation of cyclopropanes was attempted with an addition of hydrogen source, like water or isopropanol. However, only stoichiometric reactions were observed. ; 本論文主要報告利用銥卟啉輔助進行的碳碳鍵化學鍵活化以及轉化。論文分為兩部分：（1）利用雙核銥卟啉-卟啉二聯體作為碳碳鍵活化的催化劑，和(2)利用銥卟啉實現的區域選擇環丙烷當量碳碳鍵活化 。 ; 論文的第一部分描述了一系列卟啉-卟啉二聯體，包括與肽鍵聯結兩個卟啉部分的卟啉-卟啉二聯體。那些卟啉-卟啉二聯體進行金屬化作用轉化成為雙核銥卟啉-卟啉二聯體配合物。那些雙核銥卟啉-卟啉二聯體配合物 用作催化劑對於用水作為氫源的[2.2] 二聚對二甲苯的碳碳(sp 3-sp 3)單鍵加氫反應的反應性進行研究。當中發現肽鍵核銥卟啉-卟啉二聯體配合物有展現較差的催化活性 ，因為在高溫環境下酰胺鍵在有水環境進行水解。 ; 論文的第二 部分 描述了 氫化銥卟啉與環丙烷進行當量開環碳碳鍵活化。研究結果發現環丙烷當量開環的位置特定選擇性是由最弱鍵碳碳離解能所決定，然後 ...